Topical composition comprising a diazonium salt-based cosmetic bonding agent

ABSTRACT

The present invention relates to cosmetic compositions that comprise: a) a safe and effective amount of a diazonium salt bonding agent having the structure                    
     wherein X represents a cosmetic benefit agent that may or may not be attached to a chemical linker; and b) a cosmetically acceptable carrier for the bonding agent wherein the composition is administered topically to mammalian proteinaceous substrates and wherein the bonding agent reacts with a protein contained in the substrate such that the bonding agent, and thus the cosmetic benefit agent, is covalently attached to the substrate. The invention further relates to methods of using the compositions described above as well as various products that include the claimed compositions.

This application claims the benefit of U.S. Provisional Application No.60/273,931 filed Mar. 7, 2001.

FIELD OF INVENTION

The present invention relates to cosmetic compositions suitable for useon mammalian skin. These compositions comprise a bonding agent capableof attaching a cosmetic benefit agent to mammalian skin. In particular,the bonding agent is a diazonium salt linked to the cosmetic benefitagents that are then in turn linked directly or indirectly to the skin.

BACKGROUND

It is well known in the skin beauty care field that cosmetic benefitagents may be topically applied to human skin. There are a number ofbenefit agents that can be applied to the skin for varying purposesincluding moisturizers, humectants, color cosmetics, etc. There is,however, a common problem that arises in each of these areas. Theproblem is the lack of substantivity of the cosmetic benefit agents tothe skin to which they are applied. That is, the benefit agents that areapplied fail to “stick” to the skin such that a longwear result isachieved to any noticeable extent.

The present invention seeks to solve this substantivity deficiency thatis typical in topically applied products by utilizing a chemical hookbased technology. The operative chemical hook of the present inventionis a diazonium salt bonding agent that serves as a gluing mechanismbetween a cosmetic benefit agent of interest and one or more proteinmolecules that are found in the skin. In particular, Applicants havefound that diazonium salts serve as suitable bonding agents such thatimproved substantivity of various benefit agents are observed on theskin.

Without being limited by theory, the chemical hook bonding agentscovalently bond to certain amino acids present in proteinaceoussubstrates like skin, cuticles, and hair to form a substantiveattachment of the desired cosmetic benefit agent to the substrate asdemonstrated by the chemical reaction that follows

wherein AA represents functional amino acids containing amino,sulfhydryl, carboxyl, or hydroxyl groups and X is defined below.

SUMMARY OF THE INVENTION

The present invention relates to cosmetic compositions that comprise: a)a safe and effective amount of a diazonium salt bonding agent having thestructure

wherein X represents a cosmetic benefit agent that may or may not beattached to a chemical linker; and b) a cosmetically acceptable carrierfor the bonding agent wherein the composition is administered topicallyto mammalian proteinaceous substrates and wherein the bonding agentreacts with a protein contained in the substrate such that the bondingagent, and thus the cosmetic benefit agent, is covalently attached tothe substrate. The invention further relates to methods of using thecompositions described above as well as various products that includethe claimed compositions.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to topical compositions capable ofdelivering substantively attached cosmetic benefit agents to mammalianskin. The essential components of these compositions are describedbelow. Also included is a nonexclusive description of various optionaland preferred components useful in embodiments of the present invention.

As used herein, “safe and effective amount” means an amount of acompound, component, or composition (as applicable) sufficient tosignificantly induce a positive effect (e.g., confer a noticeablecosmetic benefit), but low enough to avoid serious side effects, (e.g.,undue toxicity or allergic reaction), i.e., to provide a reasonablebenefit to risk ratio, within the scope of sound medical judgment.

As used herein, “cosmetic benefit agent” means a compound, material,and/or active that confers an aesthetic feature to the surface,preferably skin, to which it is applied.

As used herein, “chemical linker” refers to a hydrocarbon chain,optionally containing heteroatoms, e.g., S, N, Se, O, substituted orunsubstituted aryls, Si, SiO, siloxane “D” groups [{(CH₃)}—Si—O₃],siloxane “M” groups {(CH₃)₃}—Si—O], and siloxane “T” groups[{(CH₃)}—Si—O_(3/2)]that form a covalent bond between the cosmeticbenefit agent and the bonding agent such that a “chemical hook” isformed.

The present invention can comprise, consist of, or consist essentiallyof any of the required or optional ingredients and/or limitationsdescribed herein.

All percentages and ratios are calculated on a weight basis unlessotherwise indicated. All percentages are calculated based upon the totalcomposition unless otherwise indicated.

All molar weights are weight average molecular weights and are given inunits of grams per mole.

All ingredient levels are exclusive of solvents, by-products, or otherimpurities that may be present in commercially available sources, unlessotherwise indicated.

All measurements made are at ambient room temperature, which isapproximately 73° F., unless otherwise designated.

All documents referred to herein, including patents, patentapplications, and printed publications, are hereby incorporated byreference in their entirety in this disclosure.

Diazonium Salt Bonding Agent

The compositions of the present invention comprise a diazonium saltbonding agent having the structure

wherein X represents a cosmetic benefit agent that may or may not beattached to a chemical linker. In preferred embodiments, X may beattached to a chemical linker that acts as a connector between X and thediazonium salt bonding agent. Suitable chemical linkers include, but arenot limited to, hydrocarbon chains containing heteroatoms like S, N, Se,O, substituted or unsubstituted aryls, Si, SiO, siloxane “D” groups[{(CH₃)}—Si—O₃], siloxane “M” groups {(CH₃)₃}—O], and siloxane “T”groups [{(CH₃)}—Si—O_(3/2)], etc. In even more preferred embodiments,the chemical linker is an aryl group. It has been found that an aryllinker provides enhanced stability of the bonding agent.

The cosmetic benefit agent of the present invention is suitable forproviding therapeutic or aesthetic skin benefits by deposition andadhesion to skin. Suitable cosmetic agents include, but are not limitedto those selected from the group consisting of absorbents, anti-acneactives, anti-caking agents, anti-cellulite agents, anti-foaming agents,anti-fungal actives, anti-inflammatory actives, anti-microbial actives,anti-oxidants, antiperspirant/deodorant actives, anti-skin atrophyactives, anti-viral agents, anti-wrinkle actives, artificial tanningagents and accelerators, astringents, barrier repair agents, binders,buffering agents, bulking agents, chelating agents, colorants, dyes,enzymes, essential oils, film formers, flavors, fragrances, humectants,hydrocolloids, light diffusers, nail enamels, opacifying agents, opticalbrighteners, optical modifiers, particulates, perfumes, pH adjusters,sequestering agents, skin conditioners/moisturizers, skin feelmodifiers, skin protectants, skin sensates, skin treating agents, skinexfoliating agents, skin lightening agents, skin soothing and/or healingagents, skin thickeners, sunscreen actives, topical anesthetics, vitamincompounds, and combinations thereof. Cosmetic benefit agents of thepresent invention are substantially free of antimicrobial polymers. Inparticular, such agents are not intended include biguanide polymers. Asused herein, “substantially free” means that the ingredient is includedin such an amount that is not readily detectable by conventionalmethods.

Suitable colorants include those used in foundations, blushes, blemishcovering compositions, and other typical color cosmetic products. Suchagents, in effect, result in cosmetic composition that is suitable formake-up application.

The cosmetic benefit agents of the present invention are well suited andcapable of attaching (either removably or fixably) to the bonding agentvia the chemical linker. In preferred embodiments, the compositions ofthe present invention comprise from about 0.001% to about 50%, by weightof the composition, of a combination of the bonding agent and thecosmetic benefit agent. In fact, even more preferred amounts of thecombination in increasing order of preference are from about 0.01% toabout 35%, 0.1% to about 20%, 0.1% to about 15%, 1% to about 10%, and 2%to about 7%, by weight of the composition. Furthermore, in suchcombinations it is preferred that the combination of the bonding agentand cosmetic benefit agent comprise from about 10% to about 90%, byweight of the combination, of the cosmetic benefit agent. Morepreferably, the combination comprises from about 20% to about 90%, ofthe cosmetic benefit agent. Even more preferably, the combinationcomprises from about 30% to 85%, of the cosmetic benefit agent. Stillmore preferably, the combination comprises about 50% of the cosmeticbenefit agent. Suitable cosmetic benefit agents include but are notlimited to those that follow.

Hydrophobic Conditioning Agents

The cosmetic benefit agent may be one or more hydrophobic conditioningagents. Preferably, the weighted arithmetic mean solubility parameter ofthe hydrophobic conditioning agent is less than or equal to 10.5. It isrecognized, based on this mathematical definition of solubilityparameters, that it is possible, for example, to achieve the requiredweighted arithmetic mean solubility parameter, i.e., less than or equalto 10.5, for a hydrophobic conditioning agent comprising two or morecompounds if one of the compounds has an individual solubility parametergreater than 10.5.

Solubility parameters are well known to the formulation chemist ofordinary skill in the art and are routinely used as a guide fordetermining compatibilities and solubilities of materials in theformulation process.

The solubility parameter of a chemical compound, δ, is defined as thesquare root of the cohesive energy density for that compound. Typically,a solubility parameter for a compound is calculated from tabulatedvalues of the additive group contributions for the heat of vaporizationand molar volume of the components of that compound, using the followingequation:$\delta = \left\lbrack \frac{\sum\limits_{i}E_{i}}{\sum\limits_{i}m_{i}} \right\rbrack^{1/2}$

wherein

Σ_(i)E_(i)=the sum of the heat of vaporization additive groupcontributions, and

Σ_(i)m_(i)=the sum of the molar volume additive group contributionsStandard tabulations of heat of vaporization and molar volume additivegroup contributions for a wide variety of atoms and groups of atoms arecollected in Barton, A. F. M. Handbook of Solubility Parameters, CRCPress, Chapter 6, Table 3, pp. 64—66 (1985. The above solubilityparameter equation is described in Fedors, R. F., “A Method forEstimating Both the Solubility Parameters and Molar Volumes of Liquids”,Polymer Enqineering and Science, vol. 14, no. 2, pp. 147-154 (February1974).

Solubility parameters obey the law of mixtures such that the solubilityparameter for a mixture of materials is given by the weighted arithmeticmean (i.e. the weighted average) of the solubility parameters for eachcomponent of that mixture. See, Handbook of Chemistry and Physics, 57thedition, CRC Press, p. C-726 (1976-1977.

Solubility parameters have also been tabulated for a wide variety ofchemical materials. Tabulations of solubility parameters are found inthe above-cited Handbook of Solubility Parameters. Also, see “SolubilityEffects In Product, Package, Penetration, And Preservation”, C. D.Vaughan, Cosmetics and Toiletries, vol. 103, October 1988, pp. 47-69.

Nonlimiting examples of hydrophobic conditioning agents include thoseselected from the group consisting of mineral oil, petrolatum, lecithin,hydrogenated lecithin, lanolin, lanolin derivatives, C7-C40 branchedchain hydrocarbons, C1-C30 alcohol esters of C1-C30 carboxylic acids,C1-C30 alcohol esters of C2-C30 dicarboxylic acids, monoglycerides ofC1-C30 carboxylic acids, diglycerides of C1-C30 carboxylic acids,triglycerides of C1-C30 carboxylic acids, ethylene glycol monoesters ofC1-C30 carboxylic acids, ethylene glycol diesters of C1-C30 carboxylicacids, propylene glycol monoesters of C1-C30 carboxylic acids, propyleneglycol diesters of C1-C30 carboxylic acids, C1-C30 carboxylic acidmonoesters and polyesters of sugars, polydialkylsiloxanes,polydiarylsiloxanes, polyalkarylsiloxanes, cylcomethicones having 3 to 9silicon atoms, vegetable oils, hydrogenated vegetable oils,polypropylene glycol C4-C20 alkyl ethers, di C8-C30 alkyl ethers, andcombinations thereof.

Straight and branched chain hydrocarbons having from about 7 to about 40carbon atoms are useful herein. Nonlimiting examples of thesehydrocarbon materials include dodecane, isododecane, squalane,cholesterol, hydrogenated polyisobutylene, docosane (i.e. a C₂₂hydrocarbon), hexadecane, isohexadecane (a commercially availablehydrocarbon sold as Permethyl® 101A by Presperse, South Plainfield,N.J.). C7-C40 isoparaffins, a class of C7-C40 branched hydrocarbons, areuseful herein. Polydecene, a branched liquid hydrocarbon, is also usefulherein and is commercially available under the tradenames Puresyn 100®and Puresyn 3000® from Mobile Chemical (Edison, N.J.).

Also useful are C1-C30 alcohol esters of C1-C30 carboxylic acids and ofC2-C30 dicarboxylic acids, including straight and branched chainmaterials as well as aromatic derivatives. Also useful are esters suchas monoglycerides of C1-C30 carboxylic acids, diglycerides of C1-C30carboxylic acids, triglycerides of C1-C30 carboxylic acids, ethyleneglycol monoesters of C1-C30 carboxylic acids, ethylene glycol diestersof C1-C30 carboxylic acids, propylene glycol monoesters of C1-C30carboxylic acids, and propylene glycol diesters of C1-C30 carboxylicacids. Straight chain, branched chain and aryl carboxylic acids areincluded herein. Also useful are propoxylated and ethoxylatedderivatives of these materials. Nonlimiting examples include diisopropylsebacate, diisopropyl adipate, isopropyl myristate, isopropyl palmitate,myristyl propionate, ethylene glycol distearate, 2-ethylhexyl palmitate,isodecyl neopentanoate, di-2-ethylhexyl maleate, cetyl palmitate,myristyl myristate, stearyl stearate, cetyl stearate, behenyl behenrate,dioctyl maleate, dioctyl sebacate, diisopropyl adipate, cetyl octanoate,diisopropyl dilinoleate, carpylic/capric triglyceride, PEG-6caprylic/capric triglyceride, PEG-8 caprylic/capric triglyceride, andcombinations thereof.

Also useful are various C1-C30 monoesters and polyesters of sugars andrelated materials. These esters are derived from a sugar or polyolmoiety and one or more carboxylic acid moieties. Depending on theconstituent acid and sugar, these esters can be in either liquid orsolid form at room temperature. Examples of liquid esters include:glucose tetraoleate, the glucose tetraesters of soybean oil fatty acids(unsaturated), the mannose tetraesters of mixed soybean oil fatty acids,the galactose tetraesters of oleic acid, the arabinose tetraesters oflinoleic acid, xylose tetralinoleate, galactose pentaoleate, sorbitoltetraoleate, the sorbitol hexaesters of unsaturated soybean oil fattyacids, xylitol pentaoleate, sucrose tetraoleate, sucrose pentaoletate,sucrose hexaoleate, sucrose hepatoleate, sucrose octaoleate, andmixtures thereof. Examples of solid esters include: sorbitol hexaesterin which the carboxylic acid ester moieties are palmitoleate andarachidate in a 1:2 molar ratio; the octaester of raffinose in which thecarboxylic acid ester moieties are linoleate and behenate in a 1:3 molarratio; the heptaester of maltose wherein the esterifying carboxylic acidmoieties are sunflower seed oil fatty acids and lignocerate in a 3:4molar ratio; the octaester of sucrose wherein the esterifying carboxylicacid moieties are oleate and behenate in a 2:6 molar ratio; and theoctaester of sucrose wherein the esterifying carboxylic acid moietiesare laurate, linoleate and behenate in a 1:3:4 molar ratio. A preferredsolid material is sucrose polyester in which the degree ofesterification is 7-8, and in which the fatty acid moieties are C18mono- and/or di-unsaturated and behenic, in a molar ratio ofunsaturates: behenic of 1:7 to 3:5. A particularly preferred solid sugarpolyester is the octaester of sucrose in which there are about 7 behenicfatty acid moieties and about 1 oleic acid moiety in the molecule. Othermaterials include cottonseed oil or soybean oil fatty acid esters ofsucrose. The ester materials are further described in, U.S. Pat. Nos.2,831,854, 4,005,196, to Jandacek, issued Jan. 25, 1977; U.S. Pat. No.4,005,195, to Jandacek, issued Jan. 25, 1977, U.S. Pat. No. 5,306,516,to Letton et al., issued Apr. 26, 1994; U.S. Pat. No. 5,306,515, toLetton et al., issued Apr. 26, 1994; U.S. Pat. No. 5,305,514, to Lettonet al., issued Apr. 26, 1994; U.S. Pat. No. 4,797,300, to Jandacek etal., issued Jan. 10, 1989; U.S. Pat. No. 3,963,699, to Rizzi et al,issued Jun. 15, 1976; U.S. Pat. No. 4,518,772, to Volpenhein, issued May21, 1985; and U.S. Pat. No. 4,517,360, to Volpenhein, issued May 21,1985.

Nonvolatile silicones such as polydialkylsiloxanes, polydiarylsiloxanes,and polyalkarylsiloxanes are also useful oils. These silicones aredisclosed in U.S. Pat. No. 5,069,897, to Orr, issued Dec. 3, 1991. Thepolyalkylsiloxanes correspond to the general chemical formulaR₃SiO[R₂SiO]_(x)SiR₃ wherein R is an alkyl group (preferably R is methylor ethyl, more preferably methyl) and x is an integer up to about 500,chosen to achieve the desired molecular weight. Commercially availablepolyalkylsiloxanes include the polydimethylsiloxanes, which are alsoknown as dimethicones, nonlimiting examples of which include theVicasil® series sold by General Electric Company and the Dow Corning®200 series sold by Dow Corning Corporation. Specific examples ofpolydimethylsiloxanes useful herein include Dow Corning® 225 fluidhaving a viscosity of 10 centistokes and a boiling point greater than200° C., and Dow Corning® 200 fluids having viscosities of 50, 350, and12,500 centistokes, respectively, and boiling points greater than 200°C. Also useful are materials such as trimethylsiloxysilicate, which is apolymeric material corresponding to the general chemical formula[(CH₂)₃SiO_(1/2)]_(x) [SiO₂]y, wherein x is an integer from about 1 toabout 500 and y is an integer from about 1 to about 500. A commerciallyavailable trimethylsiloxysilicate is sold as a mixture with dimethiconeas Dow Corning® 593 fluid. Also useful herein are dimethiconols, whichare hydroxy terminated dimethyl silicones. These materials can berepresented by the general chemical formulas R₃SiO[R₂SiO]_(x)SiR₂OH andHOR₂SiO[R₂SiO]_(x)SiR₂OH wherein R is an alkyl group (preferably R ismethyl or ethyl, more preferably methyl) and x is an integer up to about500, chosen to achieve the desired molecular weight. Commerciallyavailable dimethiconols are typically sold as mixtures with dimethiconeor cyclomethicone (e.g. Dow Corning® 1401, 1402, and 1403 fluids). Alsouseful herein are polyalkylaryl siloxanes, with polymethylphenylsiloxanes having viscosities from about 15 to about 65 centistokes at25° C. being preferred. These materials are available, for example, asSF 1075 methylphenyl fluid (sold by General Electric Company) and 556Cosmetic Grade phenyl trimethicone fluid (sold by Dow CorningCorporation). Alkylated silicones such as methyldecyl silicone andmethyloctyl silicone are useful herein and are commercially availablefrom General Electric Company. Also useful herein are alkyl modifiedsiloxanes such as alkyl methicones and alkyl dimethicones wherein thealkyl chain contains 10 to 50 carbons. Such siloxanes are commerciallyavailable under the tradenames ABIL WAX 9810 (C₂₄-C₂₈ alkyl methicone)(sold by Goldschmidt) and SF1632 (cetearyl methicone)(sold by GeneralElectric Company). Cyclomethicone/dimethicone copolyol mixtures are alsoparticularly useful as formulation aid/conditioning agents. A suitablemixture is sold under the tradename DC 3225Q®.

Vegetable oils and hydrogenated vegetable oils are also useful herein.Examples of vegetable oils and hydrogenated vegetable oils includesafflower oil, castor oil, coconut oil, cottonseed oil, menhaden oil,palm kernel oil, palm oil, peanut oil, soybean oil, rapeseed oil,linseed oil, rice bran oil, pine oil, sesame oil, sunflower seed oil,hydrogenated safflower oil, hydrogenated castor oil, hydrogenatedcoconut oil, hydrogenated cottonseed oil, hydrogenated menhaden oil,hydrogenated palm kernel oil, hydrogenated palm oil, hydrogenated peanutoil, hydrogenated soybean oil, hydrogenated rapeseed oil, hydrogenatedlinseed oil, hydrogenated rice bran oil, hydrogenated sesame oil,hydrogenated sunflower seed oil, and mixtures thereof.

Also useful are C4-C20 alkyl ethers of polypropylene glycols, C1-C20carboxylic acid esters of polypropylene glycols, and di-C8-C30 alkylethers. Nonlimiting examples of these materials include PPG-14 butylether, PPG-15 stearyl ether, dioctyl ether, dodecyl octyl ether, andmixtures thereof.

Hydrophobic chelating agents are also useful herein as hydrophobicconditioning agents. Suitable agents are described in U.S. Pat. No.4,387,244, issued to Scanlon et al. on Jun. 7, 1983, and copending U.S.patent application Ser. Nos. 09/258,747 and 09/259,485, filed in thenames of Schwartz et al. on Feb. 26, 1999.

Preferred hydrophobic conditioning agents are selected from the groupconsisting of mineral oil, petrolatum, lecithin, hydrogenated lecithin,lanolin, lanolin derivatives, C7-C40 branched chain hydrocarbons, C1-C30alcohol esters of C1-C30 carboxylic acids, C1-C30 alcohol esters ofC2-C30 dicarboxylic acids, monoglycerides of C1-C30 carboxylic acids,diglycerides of C1-C30 carboxylic acids, triglycerides of C1-C30carboxylic acids, ethylene glycol monoesters of C1-C30 carboxylic acids,ethylene glycol diesters of C1-C30 carboxylic acids, propylene glycolmonoesters of C1-C30 carboxylic acids, propylene glycol diesters ofC1-C30 carboxylic acids, C1-C30 carboxylic acid monoesters andpolyesters of sugars, polydialkylsiloxanes, polydiarylsiloxanes,polyalkylarylsiloxanes, cylcomethicones having 3 to 9 silicon atoms,vegetable oils, hydrogenated vegetable oils, polypropylene glycol C4-C20alkyl ethers, di C8-C30 alkyl ethers, and combinations thereof.

Hydrophilic Conditioning Agents

The cosmetic benefit agents of the present invention can also be one ormore hydrophilic conditioning agents. Nonlimiting examples ofhydrophilic conditioning agents include those selected from the groupconsisting of polyhydric alcohols, polypropylene glycols, polyethyleneglycols, ureas, pyrolidone carboxylic acids, ethoxylated and/orpropoxylated C3-C6 diols and triols, alpha-hydroxy C2-C6 carboxylicacids, ethoxylated and/or propoxylated sugars, polyacrylic acidcopolymers, sugars having up to about 12 carbons atoms, sugar alcoholshaving up to about 12 carbon atoms, and mixtures thereof. Specificexamples of useful hydrophilic conditioning agents include materialssuch as urea; guanidine; glycolic acid and glycolate salts (e.g.,ammonium and quaternary alkyl ammonium); lactic acid and lactate salts(e.g., ammonium and quaternary alkyl ammonium); sucrose, fructose,glucose, eruthrose, erythritol, sorbitol, mannitol, glycerol,hexanetriol, propylene glycol, butylene glycol, hexylene glycol, and thelike; polyethylene glycols such as PEG-2, PEG-3, PEG-30, PEG-50,polypropylene glycols such as PPG-9, PPG-12, PPG-15, PPG-17, PPG-20,PPG-26, PPG-30, PPG-34; alkoxylated glucose; hyaluronic acid; cationicskin conditioning polymers (e.g., quaternary ammonium polymers such asPolyquatemium polymers); and mixtures thereof. Glycerol, in particular,is a preferred hydrophilic conditioning agent in the articles of thepresent invention. Also useful are materials such as aloe vera in any ofits variety of forms (e.g., aloe vera gel), chitosan and chitosanderivatives, e.g., chitosan lactate, lactamide monoethanolamine;acetamide monoethanolamine; and mixtures thereof. Also useful arepropoxylated glycerols as described in propoxylated glycerols describedin U.S. Pat. No. 4,976,953, to Orr et al., issued Dec. 11, 1990.

Structured Conditioning Agents

The cosmetic benefit agents of the present invention may also bestructured conditioning agents. Suitable structured conditioning agentsinclude, but are not limited to, vesicular structures such as ceramides,liposomes, and the like.

Coacervates

The cosmetic benefit agents of the present invention can becoacervate-forming. Preferably, the coacervate-forming cosmetic benefitagent comprises a cationic polymer, an anionic surfactant, and adermatologically acceptable carrier for the polymer and surfactant. Thecationic polymer may be selected from the group consisting of naturalbackbone quaternary ammonium polymers, synthetic backbone quaternaryammonium polymers, natural backbone amphoteric type polymers, syntheticbackbone amphoteric type polymers, and combinations thereof.

More preferably, the cationic polymer is selected from the groupconsisting of natural backbone quaternary ammonium polymers selectedfrom the group consisting of Polyquaternium-4, Polyquaternium-10,Polyquaternium-24, PG-hydroxyethylcellulose alkyldimonium chlorides,guar hydroxypropyltrimonium chloride, hydroxypropylguarhydroxypropyltrimonium chloride, and combinations thereof; syntheticbackbone quaternary ammonium polymers selected from the group consistingof Polyquaternium-2, Polyquaternium-6, Polyquaternium-7,Polyquaternium-11, Polyquaternium-16, Polyquaternium-17,Polyquaternium-18, Polyquaternium-28, Polyquaternium-32,Polyquaternium-37, Polyquaternium-43, Polyquaternium-44,Polyquaternium-46, polymethacylamidopropyl trimonium chloride,acrylamidopropyl trimonium chloride/acrylamide copolymer, andcombinations thereof; natural backbone amphoteric type polymers selectedfrom the group consisting of chitosan, quaternized proteins, hydrolyzedproteins, and combinations thereof; synthetic backbone amphoteric typepolymers selected from the group consisting of Polyquaternium-22,Polyquaternium-39, Polyquaternium-47, adipicacid/dimethylaminohydroxypropyl diethylenetriamine copolymer,polyvinylpyrrolidone/dimethylyaminoethyl methacyrlate copolymer,vinylcaprolactam/ polyvinylpyrrolidone/dimethylaminoethylmethacrylatecopolymer, vinaylcaprolactam/polyvinylpyrrolidone/dimethylaminopropylmethacrylamide terpolymer,polyvinylpyrrolidone/dimethylaminopropylmethacrylamide copolymer,polyamine, and combinations thereof; and combinations thereof. Even morepreferably, the cationic polymer is a synthetic backbone amphoteric typepolymer. Even still more preferably, the cationic polymer is apolyamine.

When the cationic polymer is a polyamine, it is preferred that thecationic polyamine polymer be selected from the group consisting ofpolyethyleneimines, polyvinylamines, polypropyleneimines, polylysinesand combinations thereof. Even more preferably, the cationic polyaminepolymer is a polyethyleneimine.

In certain embodiments in which the cationic polymer is a polyamine, thepolyamine may be hydrophobically or hydrophilically modified. In thisinstance, the cationic polyamine polymer is selected from the groupconsisting of benzylated polyamines, ethoxylated polyamines,propoxylated polyamines, alkylated polyamines, amidated polyamines,esterified polyamines and combinations thereof. The compositioncomprises from about 0.01% to about 20%, more preferably from about0.05% to about 10%, and most preferably from about 0.1% to about 5%, byweight of the composition, of the cationic polymer.

Preferably, for the coacervate-forming cosmetic benefit agent, theanionic surfactant is selected from the group consisting ofsarcosinates, glutamates, sodium alkyl sulfates, ammonium alkylsulfates, sodium alkyleth sulfates, ammonium alkyleth sulfates, ammoniumlaureth-n-sulfates, sodium laureth-n-sulfates, isethionates,glycerylether sulfonates, sulfosuccinates and combinations thereof. Morepreferably, the anionic surfactant is selected from the group consistingof sodium lauroyl sarcosinate, monosodium lauroyl glutamate, sodiumalkyl sulfates, ammonium alkyl sulfates, sodium alkyleth sulfates,ammonium alkyleth sulfates, and combinations thereof.

Suitable coacervate-forming agents are further described in copendingU.S. patent applications Ser. No. 09/397,747, filed in the name ofSchwartz et al.; Ser. No. 09/397,746, filed in the name of Heinrich etal.; Ser. No. 09/397,712, filed in the name of Schwartz et al.; Ser. No.09/397,723, filed in the name of Heinrich et al.; and Ser. No.09/397,722, filed in the name of Venkitaraman et al.; each of which werefiled on Sep. 16, 1999.

Alternatively, the coacervate-forming cosmetic benefit agent maycomprise an anionic polymer, a cationic surfactant, and adermatologically acceptable carrier for the polymer and surfactant. Theanionic polymer may be selected from the group consisting of polyacrylicacid polymers, polyacrylamide polymers, copolymers of acrylic acid,acrylamide, and other natural or synthetic polymers (e.g., polystyrene,polybutene, polyurethane, etc.), naturally derived gums, andcombinations thereof. Suitable gums include alginates (e.g., propyleneglycol alginate), pectins, chitosans (e.g., chitosan lactate), andmodified gums (e.g., starch octenyl succinate), and combinationsthereof. More preferably, the anionic polymer is selected from the groupconsisting of polyacrylic acid polymers, polyacrylamide polymers,pectins, chitosans, and combinations thereof. Suitable cationicsurfactants include, but are not limited to, those discussed herein.

Colorants

The present compositions may comprise a bonding agent that comprises oneor more colorants. Suitable colorants include, but are not limited to,pigments, dyes or lakes or a combination thereof as the cosmetic benefitagents. Preferred pigments include, but are not limited to, iron oxides,and titanium oxides. Suitable dyes include FD&C approved colorants, D&Capproved colorants, and those approved for use in Europe and Japan. See,Marmion, D. M., Handbook of US Colorants for Food, Drugs, Cosmetics,.and Medical Devices, 3rd ed, 1991.

Vitamin Compounds

The present compositions may comprise vitamin compounds, precursors, andderivatives thereof as the cosmetic benefit agents. These vitamincompounds may be in either natural or synthetic form. Suitable vitamincompounds include, but are not limited to, Vitamin A (e.g., betacarotene, retinoic acid, retinol, retinoids, retinyl palmitate, retinylproprionate, etc.), Vitamin B (e.g., niacin, niacinamide, riboflavin,pantothenic acid, etc.), Vitamin C (e.g., ascorbic acid, etc.), VitaminD (e.g., ergosterol, ergocalciferol, cholecalciferol, etc.), Vitamin E(e.g., tocopherol acetate, etc.), and Vitamin K (e.g., phytonadione,menadione, phthiocol, etc.) compounds.

For instance, vitamin B₃ compounds are particularly useful forregulating skin condition as described in co-pending U.S. applicationSer. No. 08/834,010, filed Apr. 11, 1997 (corresponding to internationalpublication WO 97/39733 A1, published Oct. 30, 1997) which isincorporated by reference herein in its entirety. The compositions ofthe present invention preferably comprise from about 0.01% to about 50%,more preferably from about 0.1% to about 10%, even more preferably fromabout 0.5% to about 10%, and still more preferably from about 1% toabout 5%, most preferably from about 2% to about 5%, of the vitamin B₃compound.

As used herein, “vitamin B₃ compound” means a compound having theformula:

wherein R is —CONH₂ (i.e., niacinamide), —COOH (i.e., nicotinic acid) or—CH₂OH (i.e., nicotinyl alcohol); derivatives thereof; and salts of anyof the foregoing.

Exemplary derivatives of the foregoing vitamin B₃ compounds includenicotinic acid esters, including non-vasodilating esters of nicotinicacid, nicotinyl amino acids, nicotinyl alcohol esters of carboxylicacids, nicotinic acid N-oxide and niacinamide N-oxide.

Examples of suitable vitamin B₃ compounds are well known in the art andare commercially available from a number of sources, e.g., the SigmaChemical Company (St. Louis, Mo.); ICN Biomedicals, Inc. (Irvin, Calif.)and Aldrich Chemical Company (Milwaukee, Wis.).

The vitamin compounds may be included as the substantially purematerial, or as an extract obtained by suitable physical and/or chemicalisolation from natural (e.g., plant) sources.

Anti-Acne Actives

Examples of useful anti-acne actives as the cosmetic benefit agents ofthe present invention include, but are not limited to, the keratolyticssuch as salicylic acid (o-hydroxybenzoic acid), derivatives of salicylicacid such as 5-octanoyl salicylic acid, and resorcinol; retinoids suchas retinoic acid and its derivatives (e.g., cis and trans);sulfur-containing D and L amino acids and their derivatives and salts,particularly their N-acetyl derivatives, a preferred example of which isN-acetyl-L-cysteine; lipoic acid; antibiotics and antimicrobials such asbenzoyl peroxide, octopirox, tetracycline, 2,4,4′-trichloro-2′-hydroxydiphenyl ether, 3,4,4′-trichlorobanilide, azelaic acid and itsderivatives, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, ethylacetate, clindamycin and meclocycline; sebostats such as flavonoids; andbile salts such as scymnol sulfate and its derivatives, deoxycholate,and cholate.

Anti-Wrinkle and Anti-Skin Atrophy Actives

Examples of anti-wrinkle and anti-skin atrophy actives useful as thecosmetic benefit agents of the present invention include, but are notlimited to, retinoic acid and its derivatives (e.g., cis and trans);retinol; retinyl esters; niacinamide, and derivatives thereof;sulfur-containing D and L amino acids and their derivatives and salts,particularly the N-acetyl derivatives, a preferred example of which isN-acetyl-L-cysteine; thiols, e.g., ethane thiol; terpene alcohols (e.g.,farnesol); hydroxy acids, phytic acid, lipoic acid; lysophosphatidicacid, alpha-hydroxy acids (e.g., lactic acid and glycolic acid),beta-hydroxy acids (e.g., salicylic acid), and skin peel agents (e.g.,phenol and the like).

Enzymes

The cosmetic benefit agents of the present invention may be one or moreenzymes. Preferably, such enzymes are dermatologically acceptable.Suitable enzymes include, but are not limited to, keratinase, protease,amylase, subtilisin, other peptides and proteins, etc.

Peptides, including but not limited to, di-, tri-, tetra-, andpentapeptides and derivatives thereof, may be included as the cosmeticbenefit agents of the present invention in amounts that are safe andeffective. As used herein, “peptides” refers to both the naturallyoccuring peptides and synthesized peptides. Also useful herein arenaturally occurring and commercially available compositions that containpeptides.

Sunscreen Actives

Also useful herein as cosmetic benefit agents are sunscreening actives.A wide variety of sunscreening agents are described in U.S. Pat. No.5,087,445, to Haffey et al., issued Feb. 11, 1992; U.S. Pat. No.5,073,372, to Turner et al., issued Dec. 17, 1991; U.S. Pat. No.5,073,371, to Turner et al. issued Dec. 17, 1991; and Sagarin, et al.,at Chapter VIII, pages 189 et seq., of Cosmetics Science and Technology.Nonlimiting examples of sunscreens which are useful in the compositionsof the present invention are those selected from the group consisting of2-ethylhexyl p-methoxycinnamate, 2-ethylhexylN,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid,2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone,homomenthyl salicylate, octyl salicylate,4,4′-methoxy-t-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane,3-benzylidene camphor, 3-(4-methylbenzylidene)camphor, titanium dioxide,zinc oxide, silica, iron oxide, and mixtures thereof. Still other usefulsunscreens are those disclosed in U.S. Pat. No. 4,937,370, to Sabatelli,issued Jun. 26, 1990; and U.S. Pat. No. 4,999,186, to Sabatelli et al.,issued Mar. 12, 1991. Especially preferred examples of these sunscreensinclude those selected from the group consisting of4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acidester with 4-hydroxydibenzoylmethane,4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of2-hydroxy-4-(2-hydroxyethoxy)benzophenone,4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof. Exact amountsof sunscreens which can be employed will vary depending upon thesunscreen chosen and the desired Sun Protection Factor (SPF) to beachieved. SPF is a commonly used measure of photoprotection of asunscreen against erythema.

Chelators

The bonding agents of the present compositions may also includechelators as the cosmetic benefit agent. As used herein, “chelator” or“chelating agent” means an active agent capable of removing a metal ionfrom a system by forming a complex so that the metal ion cannot readilyparticipate in or catalyze chemical reactions. The inclusion of achelating agent is especially useful for providing protection against UVradiation that can contribute to excessive scaling or skin texturechanges and against other environmental agents, which can cause skindamage.

A safe and effective amount of a chelating agent may be added to thecompositions of the subject invention, preferably in amounts of fromabout 0.1% to about 10%, more preferably from about 1% to about 5%, byweight of the composition. Exemplary chelators that are useful hereinare disclosed in U.S. Pat. No. 5,487,884, issued Jan. 30, 1996 toBissett et al.; International Publication No. 91/16035, Bush et al.,published Oct. 31, 1995; and International Publication No. 91/16034,Bush et al., published Oct. 31, 1995. Preferred chelators useful incompositions of the subject invention are furildioxime, furildioximederivatives, furilmonoxime, furilmonoxime derivatives, and combinationsthereof.

Flavonoids

The cosmetic benefit agents of the present invention may also be aflavonoid compound. Flavonoids are broadly disclosed in U.S. Pat. Nos.5,686,082 and 5,686,367. Flavonoids suitable for use in the presentinvention are flavanones selected from the group consisting ofunsubstituted flavanones, mono-substituted flavanones, and mixturesthereof; chalcones selected from the group consisting of unsubstitutedchalcones, mono-substituted chalcones, di-substituted chalcones,tri-substituted chalcones, and mixtures thereof; flavones selected fromthe group consisting of unsubstituted flavones, mono-substitutedflavones, di-substituted flavones, and mixtures thereof; one or moreisoflavones; coumarins selected from the group consisting ofunsubstituted coumarins, mono-substituted coumarins, di-substitutedcoumarins, and mixtures thereof; chromones selected from the groupconsisting of unsubstituted chromones, mono-substituted chromones,di-substituted chromones, and mixtures thereof; one or more dicoumarols;one or more chromanones; one or more chromanols; isomers (e.g.,cis/trans isomers) thereof; and mixtures thereof. By the term“substituted” as used herein means flavonoids wherein one or morehydrogen atom of the flavonoid has been independently replaced withhydroxyl, C1-C8 alkyl, C1-C4 alkoxyl, O-glycoside, and the like or amixture of these substituents.

Examples of suitable flavonoids include, but are not limited to,unsubstituted flavanone, mono-hydroxy flavanones (e.g., 2′-hydroxyflavanone, 6-hydroxy flavanone, 7-hydroxy flavanone, etc.), mono-alkoxyflavanones (e.g., 5-methoxy flavanone, 6-methoxy flavanone, 7-methoxyflavanone, 4′-methoxy flavanone, etc.), unsubstituted chalcone(especially unsubstituted trans-chalcones), mono-hydroxy chalcones(e.g., 2′-hydroxy chalcone, 4′-hydroxy chalcone, etc.), dihydroxychalcones (e.g., 2′,4-dihydroxy chalcone, 2′,4′-dihydroxy chalcone,2,2′-dihydroxy chalcone, 2′,3-dihydroxy chalcone, 2′,5′-dihydroxychalcone, etc.), and tri-hydroxy chalcones (e.g., 2′,3′,4′-trihydroxychalcone, 4,2′,4′-trihydroxy chalcone, 2,2′,4′-trihydroxy chalcone,etc.), unsubstituted flavone, 7,2′-dihydroxy flavone, 3′,4′-dihydroxynaphthoflavone, 4′-hydroxy flavone, 5,6-benzoflavone, and7,8-benzoflavone, unsubstituted isoflavone, daidzein (7,4′-dihydroxyisoflavone), 5,7-dihydroxy-4′-methoxy isoflavone, soy isoflavones (amixture extracted from soy), unsubstituted coumarin, 4-hydroxy coumarin,7-hydroxy coumarin, 6-hydroxy-4-methyl coumarin, unsubstituted chromone,3-formyl chromone, 3-formyl-6-isopropyl chromone, unsubstituteddicoumarol, unsubstituted chromanone, unsubstituted chromanol, andmixtures thereof.

Preferred for use herein are unsubstituted flavanone, methoxyflavanones, unsubstituted chalcone, 2′,4-dihydroxy chalcone, andmixtures thereof. Most preferred are unsubstituted flavanone,unsubstituted chalcone (especially the trans isomer), and mixturesthereof.

They can be synthetic materials or obtained as extracts from naturalsources (e.g., plants). The naturally sourced material can also furtherbe derivatized (e.g., a glycoside, an ester or an ether derivativeprepared following extraction from a natural source). Flavonoidcompounds useful herein are commercially available from a number ofsources, e.g., Indofine Chemical Company, Inc. (Somerville, N.J.),Steraloids, Inc. (Wilton, N.H.), and Aldrich Chemical Company, Inc.(Milwaukee, Wis.).

Mixtures of the above flavonoid compounds may also be used.

The herein described flavonoid compounds are preferably present in theinstant invention at concentrations of from about 0.01% to about 20%,more preferably from about 0.1% to about 10%, and most preferably fromabout 0.5% to about 5%.

Sterols

The cosmetic benefit agents of the present invention may also be a safeand effective amount of one or more sterol compounds. Examples of usefulsterol compounds include sitosterol, stigmasterol, campesterol,brassicasterol, lanosterol, 7-dehydrocholesterol, and mixtures thereof.These can be synthetic in origin or from natural sources, e.g., blendsextracted from plant sources (e.g., phytosterols).

Anti-Cellulite Agents

The cosmetic benefit agent may also be an anti-cellulite agent. Suitableagents may include, but are not limited to, xanthine compounds (e.g.,caffeine, theophylline, theobromine, and aminophylline), forskolin, andderivatives thereof.

Skin Lightening Agents

Another suitable cosmetic benefit agent is a skin lightening agent. Whenused, the compositions preferably comprise from about 0.1% to about 10%,more preferably from about 0.2% to about 5%, also preferably from about0.5% to about 2%, by weight of the composition, of a skin lighteningagent. Suitable skin lightening agents include those known in the art,including kojic acid, arbutin, deoxyarbutin, ascorbic acid andderivatives thereof, e.g., magnesium ascorbyl phosphate or sodiumascorbyl phosphate or other salts of ascorbyl phosphate.

Cosmetically Acceptable Carrier

The compositions of the present invention comprise acosmetically-acceptable carrier or vehicle for bonding agent and anyoptional components. Suitable carriers are well known in the art and areselected based on the end use application. For example, carriers of thepresent invention include, but are not limited to, those suitable forapplication to skin. Preferably, the carriers of the present inventionare suitable for application to skin (e.g., sunscreens, creams, milks,lotions, masks, serums, etc.) and nails (e.g., polishes, treatments,etc.). Such carriers are well-known to one of ordinary skill in the art,and can include one or more compatible liquid or solid filler diluentsor vehicles which are suitable for application to skin and nails. Theexact amount of carrier will depend upon the level of the bonding agentand any other optional ingredients that one of ordinary skill in the artwould classify as distinct from the carrier (e.g., other activecomponents). The compositions of the present invention preferablycomprise from about 75% to about 99.999%, more preferably from about 85%to about 99.99%, still more preferably from 90% to about 99%, and mostpreferably, from about 93% to about 98%, by weight of the composition,of a carrier.

The carrier and compositions herein can be formulated in a number ofways, including but not limited to emulsions (in emulsion technology, acomposition comprising a “dispersed phase” and a “continuous phase;” thedispersed phase existing as small particles or droplets that aresuspended in and surrounded by a continuous phase). For example,suitable emulsions include oil-in-water, water-in-oil,water-in-oil-in-water, oil-in-water-in-oil, and oil-in-water-in-siliconeemulsions. Preferred compositions comprise an oil-in-water emulsion.

The compositions of the present invention can be formulated into a widevariety of product types, including creams, waxes, pastes, lotions,milks, mousses, gels, oils, tonics, and sprays. Preferred compositionsare formulated into lotions, creams, gels, and sprays. These productforms may be used for a number of applications, including, but notlimited to, hand and body lotions, cold creams, facial moisturizers,anti-acne preparations, topical analgesics, make-ups/cosmetics includingfoundations, eyeshadows, lipsticks, and the like. Any additionalcomponents required to formulate such products vary with product typeand can be routinely chosen by one skilled in the art.

If compositions of the present invention are formulated as an aerosoland applied to the skin as a spray-on product, a propellant is added tothe composition. Examples of suitable propellants includechlorofluorinated lower molecular weight hydrocarbons. A more completedisclosure of propellants useful herein can be found in Sagarin,Cosmetics Science and Technology, 2nd Edition, Vol. 2, pp. 443-465(1972).

Optional Ingredients

The compositions of the present invention may contain a variety of othercomponents such as are conventionally used in a given product typeprovided that they do not unacceptably alter the benefits of theinvention. These optional components should be suitable for applicationto mammalian skin, that is, when incorporated into the compositions theyare suitable for use in contact with human skin without undue toxicity,incompatibility, instability, allergic response, and the like, withinthe scope of sound medical or formulator's judgment. The CTFA CosmeticIngredient Handbook, Second Edition (1992) describes a wide variety ofnonlimiting cosmetic and pharmaceutical ingredients commonly used in theskin care industry, which are suitable for use in the compositions ofthe present invention. Examples of these ingredient classes include:enzymes, surfactants, abrasives, skin exfoliating agents, absorbents,aesthetic components such as fragrances, pigments, colorings/colorants,essential oils, skin sensates, astringents, etc. (e.g., clove oil,menthol, camphor, eucalyptus oil, eugenol, menthyl lactate, witch hazeldistillate), anti-acne agents (e.g., resorcinol, sulfur, salicylic acid,erythromycin, zinc, etc.), anti-caking agents, antifoaming agents,antimicrobial agents (e.g., iodopropyl butylcarbamate), antioxidants,binders, biological additives, buffering agents, bulking agents,chelating agents, chemical additives, colorants, cosmetic astringents,cosmetic biocides, denaturants, drug astringents, external analgesics,polymer beads, film formers or materials, e.g., polymers, for aiding thefilm-forming properties and substantivity of the composition (e.g.,copolymer of eicosene and vinyl pyrrolidone), humectants, opacifyingagents, pH adjusters, propellants, reducing agents, sequestrants, skinbleaching agents (or lightening agents) (e.g., hydroquinone, kojic acid,ascorbic acid, magnesium ascorbyl phosphate, ascorbyl glucosamine), skinsoothing and/or healing agents (e.g., panthenol and derivatives (e.g.,ethyl panthenol), aloe vera, pantothenic acid and its derivatives,allantoin, bisabolol, and dipotassium glycyrrhizinate), thickeners,hydrocolloids, particular zeolites, and vitamins and derivatives thereof(e.g. tocopherol, tocopherol acetate, beta carotene, retinoic acid,retinol, retinoids, retinyl palmitate, niacin, niacinamide, and thelike). The compositions of the present invention may include carriercomponents such as are known in the art. Such carriers can include oneor more compatible liquid or solid filler diluents or vehicles that aresuitable for application to skin.

The optional components useful herein can be categorized by theirtherapeutic or aesthetic benefit or their postulated mode of action.However, it is to be understood that the optional components usefulherein can in some instances provide more than one therapeutic oraesthetic benefit or operate via more than one mode of action.Therefore, classifications herein are made for the sake of convenienceand are not intended to limit the component to that particularapplication or applications listed. Also, when applicable, thepharmaceutically-acceptable salts of the components are useful herein.

Non-Steroidal Anti-lnflammatory Actives (NSAIDS)

Examples of NSAIDS useful in the compositions of the present inventioninclude, but are not limited to, the following categories: propionicacid derivatives; acetic acid derivatives; fenamic acid derivatives;biphenylcarboxylic acid derivatives; and oxicams. All of these NSAIDSare fully described in U.S. Pat. No. 4,985,459 to Sunshine et al.,issued Jan. 15, 1991. Examples of useful NSAIDS include acetyl salicylicacid, ibuprofen, naproxen, benoxaprofen, flurbiprofen, fenoprofen,fenbufen, ketoprofen, indoprofen, pirprofen, carprofen, oxaprozin,pranoprofen, miroprofen, tioxaprofen, suprofen, alminoprofen,tiaprofenic acid, fluprofen and bucloxic acid. Also useful are thesteroidal anti-inflammatory drugs including hydrocortisone and the like.

Topical Anesthetics

Examples of topical anesthetic drugs suitable for inclusion in thecompositions of the present invention include, but are not limited to,benzocaine, lidocaine, bupivacaine, chlorprocaine, dibucaine,etidocaine, mepivacaine, tetracaine, dyclonine, hexylcaine, procaine,cocaine, ketamine, pramoxine, phenol, and pharmaceutically acceptablesalts thereof.

Artificial Tanning Actives and Accelerators

Examples of artificial tanning actives and accelerators useful in thecompositions of the present invention include, but are not limited to,dihydroxyacetaone, tyrosine, tyrosine esters such as ethyl tyrosinate,and phospho-DOPA.

Antimicrobial and Antifungal Actives

Examples of antimicrobial and antifungal actives useful in thecompositions of the present invention include, but are not limited to,β-lactam drugs, quinolone drugs, ciprofloxacin, norfloxacin,tetracycline, erythromycin, amikacin, 2,4,4′-trichloro-2′-hydroxydiphenyl ether, 3,4,4′-trichlorocarbanilide, phenoxyethanol, phenoxypropanol, phenoxyisopropanol, doxycycline, capreomycin, chlorhexidine,chlortetracycline, oxytetracycline, clindamycin, ethambutol, hexamidineisethionate, metronidazole, pentamidine, gentamicin, kanamycin,lineomycin, methacycline, methenamine, minocycline, neomycin,netilmicin, paromomycin, streptomycin, tobramycin, miconazole,tetracycline hydrochloride, erythromycin, zinc erythromycin,erythromycin estolate, erythromycin stearate, amikacin sulfate,doxycycline hydrochloride, capreomycin sulfate, chlorhexidine gluconate,chlorhexidine hydrochloride, chlortetracycline hydrochloride,oxytetra-cyline hydrochloride, clindamycin hydrochloride, ethambutolhydrochloride, metronidazole hydrochloride, pentamidine hydrochloride,gentamicin sulfate, kanamycin sulfate, lineomycin hydrochloride,methacycline hydrochloride, methenamine hippurate, methenaminemandelate, minocycline hydrochloride, neomycin sulfate, netilmicinsulfate, paromomycin sulfate, streptomycin sulfate, tobramycin sulfate,miconazole hydrochloride, amanfadine hydrochloride, amanfadine sulfate,octopirox, parachlorometa xylenol, nystatin, tolnaftate, zinc pyrithioneand clotrimazole.

Anti-viral Agents

The compositions of the present invention may further comprise one ormore anti-viral agents. Suitable anti-viral agents include, but are notlimited to, metal salts (e.g., silver nitrate, copper sulfate, ironchloride, etc.) and organic acids (e.g., malic acid, salicylic acid,succinic acid, benzoic acid, etc.). In particular compositions whichcontain additional suitable anti-viral agents include those described incopending U.S. patent applications Ser. No. 09/421,084 (Beerse et al.);Ser. No. 09/421,131 (Biedermann et al.); Ser. No. 09/420,646 (Morgan etal.); and Ser. No. 09/421,179 (Page et al.), which were each filed onOct. 19, 1999.

Hydrocolloids

Hydrocolloids are well known in the art and are helpful in extending theuseful life of the surfactants. Thus, these would be useful forinclusion particularly in those embodiments intended for cleansing theskin, e.g., a showering or bathing experience. Suitable hydrocolloidsinclude, but are not limited to, xanthan gum, carboxymethyl cellulose,hydroxyethyl cellulose, hydroxylpropyl cellulose, methyl and ethylcellulose, natural gums, gudras guar gum, bean gum, natural starches,deionitized starches (e.g., starch octenyl succinate) and the like.

Oil-soluble Polymeric Gelling Agents

The compositions of the present invention may optionally comprise one ormore polymeric materials that are oil-soluble and form a gel withhydrophobic materials (e.g. oils) that are contained in thecompositions. Such polymers are beneficial for structuring thesematerials resulting in flexible gels with improved stability andshear-resistance.

Particularly suitable are at least partially cross-linked oil-solublepolymeric materials with a softening point <160° C. Suitable materialscome from the chemical groups of PE (polyethylenes), PVA (polyvinylalcohols) and derivatives, PVP (polyvinylpyrrolidones) and derivatives,PVP/Alkene Copolymers, PVP/VA copolymers, PVM/MA (methyl vinylether/maleic anhydride) copolymers and their esters and ethers,particularly poly (alkyl vinyl ether-co-maleic anhydride) copolymers,ethylene/VA copolymers, styrene/isoprene, styrene/ethylene/butylene,styrene/ethylene/propylene, styrene/ethylene/butylene/styrene andstyrene/butadiene copolymers. Suitable materials are available e.g. fromDupont (ELVAX® types), BASF (LUVISKOL® types), Shell (KRATON® polymers)and ISP (PVP, GANTREZ® and GANEX® types).

Hydrophilic Gelling Agent

The compositions of the invention can also contain a hydrophilic gellingagent at a level preferably from about 0.01% to about 10%, morepreferably from about 0.02% to about 2%, and especially from about 0.02%to about 0.5%. The gelling agent preferably has a viscosity (1% aqueoussolution, 20° C., Brookfield RVT) of at least about 4000 mPa.s, morepreferably at least about 10,000 mPa.s and especially at least 50,000mPa-s.

Suitable hydrophilic gelling agents can generally be described aswater-soluble or colloidally water-soluble polymers, and includecellulose ethers (e.g. hydroxyethyl cellulose, methyl cellulose,hydroxypropylmethyl cellulose), polyvinylpyrrolidone, polyvinylalcohol,polyquaternium-10, guar gum, hydroxypropyl guar gum and xanthan gum.

Among suitable hydrophilic gelling agents are acrylic acid/ethylacrylate copolymers and the carboxyvinyl polymers sold by the B. F.Goodrich Company under the trademark of Carbopol resins. These resinsconsist essentially of a colloidally water-soluble polyalkenyl polyethercrosslinked polymer of acrylic acid crosslinked with from 0.75% to 2.00%of a crosslinking agent such as for example polyallyl sucrose orpolyallyl pentaerythritol. Examples include Carbopol 934, Carbopol 940,Carbopol 950, Carbopol 980, Carbopol 951 and Carbopol 981. Carbopol 934is a water-soluble polymer of acrylic acid crosslinked with about 1% ofa polyallyl ether of sucrose having an average of about 5.8 allyl groupsfor each sucrose molecule. Also suitable for use herein arehydrophobically-modified cross-linked polymers of acrylic acid havingamphipathic properties available under the Trade Name Carbopol 1382,Carbopol 1342 and Pemulen TR-1 (CTFA Designation: Acrylates/10-30 AlkylAcrylate Crosspolymer). A combination of the polyalkenyl polyethercross-linked acrylic acid polymer and the hydrophobically modifiedcross-linked acrylic acid polymer is also suitable for use herein. Othersuitable gelling agents suitable for use herein are oleogels such astrihydroxystearin and aluminium magnesium hydroxy stearate. The gellingagents herein are particularly valuable for providing excellentstability characteristics over both normal and elevated temperatures.

Neutralizing agents suitable for use in neutralizing acidic groupcontaining hydrophilic gelling agents herein include sodium hydroxide,potassium hydroxide, ammonium hydroxide, monoethanolamine,diethanolamine and triethanolamine.

Surfactants

Surfactants can also be included into the compositions of the presentinvention, particularly when the compositions are useful for cleansingskin. A lathering surfactant is preferred for use in such instances. Asused herein, “lathering surfactant” means a surfactant, which whencombined with water and mechanically agitated generates a foam orlather. Such surfactants are preferred since increased lather isimportant to consumers as an indication of cleansing effectiveness. Incertain personal care embodiments, the surfactants or combinations ofsurfactants are preferably mild. As used herein, “mild” means that thesurfactants as well as to the articles of the present inventiondemonstrate skin mildness at least milder than common bar soap matricesthat typically comprise a combination of natural soap and syntheticsurfactant (e.g., Lever 2000® and Zest®). Methods for measuringmildness, or inversely the irritancy, of surfactant containing articles,are based on a skin barrier destruction test. In this test, the milderthe surfactant, the lesser the skin barrier is destroyed. Skin barrierdestruction is measured by the relative amount of radio-labeled (tritiumlabeled) water (3H-H₂O) that passes from the test solution through theskin epidermis into the physiological buffer contained in the diffusatechamber. This test is described by T. J. Franz in the J. Invest.Dermatol., 1975, 64, pp. 190-195; and in U.S. Pat. No. 4,673,525, toSmall et al., issued Jun 16, 1987. Other testing methodologies fordetermining surfactant mildness well known to one skilled in the art canalso be used.

A wide variety of lathering surfactants are useful herein and includethose selected from the group consisting of anionic latheringsurfactants, nonionic lathering surfactants, cationic latheringsurfactants, amphoteric lathering surfactants, and mixtures thereof.

Anionic Lathering Surfactants

Nonlimiting examples of anionic lathering surfactants useful herein aredisclosed in McCutcheon's, Detergents and Emulsifiers, North Americanedition (1986), published by Allured Publishing Corporation;McCutcheon's, Functional Materials, North American Edition (1992); andU.S. Pat. No. 3,929,678, to Laughlin et al., issued Dec. 30, 1975.

A wide variety of anionic surfactants are potentially useful herein.Nonlimiting examples of anionic lathering surfactants include thoseselected from the group consisting of alkyl and alkyl ether sulfates,sulfated monoglycerides, sulfonated olefins, alkyl aryl sulfonates,primary or secondary alkane sulfonates, alkyl sulfosuccinates, acyltaurates, acyl isethionates, alkyl glycerylether sulfonate, sulfonatedmethyl esters, sulfonated fatty acids, alkyl phosphates, ethoxylatedalkyl phosphates, acyl glutamates, acyl sarcosinates, alkylsulfoacetates, acylated peptides, alkyl ether carboxylates, acyllactylates, anionic fluorosurfactants, and combinations thereof.Combinations of anionic surfactants can be used effectively in thepresent invention. Specific examples of alkyl sulfates that may be usedare sodium, ammonium, potassium, magnesium, or TEA salts of lauryl ormyristyl sulfate. Examples of alkyl ether sulfates that may be usedinclude ammonium, sodium, magnesium, or TEA laureth-3 sulfate.

Another suitable class of anionic surfactants are the sulfatedmonoglycerides of the form R1CO-O-CH2-C(OH)H-CH2-O-SO3M, wherein R1 is asaturated or unsaturated, branched or unbranched alkyl group from about8 to about 24 carbon atoms, and M is a water-soluble cation such asammonium, sodium, potassium, magnesium, triethanolamine, diethanolamineand monoethanolamine. An example of a sulfated monoglyceride is sodiumcocomonoglyceride sulfate.

Other suitable anionic surfactants include olefin sulfonates of the formR1SO3M, wherein R1 is a mono-olefin having from about 12 to about 24carbon atoms, and M is a water-soluble cation such as ammonium, sodium,potassium, magnesium, triethanolamine, diethanolamine andmonoethanolamine. An example of a sulfonated olefin is sodium C14/C16alpha olefin sulfonate.

Other suitable anionic surfactants are the linear alkylbenzenesulfonates of the form R1—C6H4—SO3M, wherein R1 is a saturated orunsaturated, branched or unbranched alkyl group from about 8 to about 24carbon atoms, and M is a water-soluble cation such as ammonium, sodium,potassium, magnesium, triethanolamine, diethanolamine andmonoethanolamine. An example of this anionic surfactant is sodiumdodecylbenzene sulfonate.

Still other anionic surfactants suitable for the compositions of thepresent invention include the primary or secondary alkane sulfonates ofthe form R1SO3M, wherein R1 is a saturated or unsaturated, branched orunbranched alkyl chain from about 8 to about 24 carbon atoms, and M is awater-soluble cation such as ammonium, sodium, potassium, magnesium,triethanolamine, diethanolamine and monoethanolamine. An example of analkane sulfonate useful herein is alkali metal or ammonium C13-C17paraffin sulfonates.

Still other suitable anionic surfactants are the alkyl sulfosuccinates,which include disodium N-octadecylsulfosuccinamate; diammonium laurylsulfosuccinate; tetrasodiumN-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinate; diamyl ester of sodiumsulfosuccinic acid; dihexyl ester of sodium sulfosuccinic acid; anddioctyl esters of sodium sulfosuccinic acid.

Also useful are taurates that are based on taurine. Examples of tauratesinclude N-alkyltaurines such as the one prepared by reactingdodecylamine with sodium isethionate as detailed in U.S. Pat. No.2,658,072.

Another class of suitable anionic surfactants is the acyl isethionates.Nonlimiting examples of these acyl isethionates include ammonium cocoylisethionate, sodium cocoyl isethionate, sodium lauroyl isethionate, andmixtures thereof.

Still other suitable anionic surfactants are the alkylglyceryl ethersulfonates of the form R1—OCH2—C(OH)H—CH2—SO3M, wherein R1 is asaturated or unsaturated, branched or unbranched alkyl group from about8 to about 24 carbon atoms, and M is a water-soluble cation such asammonium, sodium, potassium, magnesium, triethanolamine, diethanolamineand monoethanolamine. One example is sodium cocoglyceryl ethersulfonate.

Other suitable anionic surfactants include:

1. sulfonated fatty acids of the form R1—CH(SO4)—COOH and sulfonatedmethyl esters of the from R1—CH(SO4)—CO—O—CH3, where R1 is a saturatedor unsaturated, branched or unbranched alkyl group from about 8 to about24 carbon atoms (e.g., alpha sulphonated coconut fatty acid and laurylmethyl ester);

2. phosphates such as monoalkyl, dialkyl, and trialkylphosphate saltsformed by the reaction of phosphorous pentoxide with monohydric branchedor unbranched alcohols having from about 8 to about 24 carbon atoms(e.g., sodium mono or dilaurylphosphate, ethoxylated monoalkylphosphates, etc.);

3. acyl glutamates corresponding to the formula R1CO—N(COOH)—CH2CH2—CO2Mwherein R1 is a saturated or unsaturated, branched or unbranched alkylor alkenyl group of about 8 to about 24 carbon atoms, and M is awater-soluble cation (e.g., sodium lauroyl glutamate and sodium cocoylglutamate);

4. alkanoyl sarcosinates corresponding to the formulaR1CON(CH3)—CH2CH2—CO2M wherein R1 is a saturated or unsaturated,branched or unbranched alkyl or alkenyl group of about 10 to about 20carbon atoms, and M is a water-soluble cation (e.g., sodium lauroylsarcosinate, sodium cocoyl sarcosinate, and ammonium lauroylsarcosinate);

5. alkyl ether carboxylates corresponding to the formulaR1—(OCH2CH2)x—OCH2—CO2M wherein R1 is a saturated or unsaturated,branched or unbranched alkyl or alkenyl group of about 8 to about 24carbon atoms, x is 1 to 10, and M is a water-soluble cation (e.g.,sodium laureth carboxylate);

6. acyl lactylates corresponding to the formulaR1CO—[O—CH(CH3)—CO]x—CO2M wherein R1 is a saturated or unsaturated,branched or unbranched alkyl or alkenyl group of about 8 to about 24carbon atoms, x is 3, and M is a water-soluble cation (e.g., sodiumcocoyl lactylate);

7. carboxylates, nonlimiting examples of which include sodium lauroylcarboxylate, sodium cocoyl carboxylate, and ammonium lauroylcarboxylate;

8. anionic flourosurfactants; and

9. natural soaps derived from the saponification of vegetable and/oranimal fats & oils exmaples of which include sodium laurate, sodiummyristate, palmitate, stearate, tallowate, cocoate.

Any counter cation, M, can be used on the anionic surfactant.Preferably, the counter cation is selected from the group consisting ofsodium, potassium, ammonium, monoethanolamine, diethanolamine, andtriethanolamine.

Nonionic Lathering Surfactants

Nonlimiting examples of nonionic lathering surfactants that mayoptionally be included in the compositions of the present invention aredisclosed in McCutcheon's, Detergents and Emulsifiers, North Americanedition (1986), published by allured Publishing Corporation; andMcCutcheon's, Functional Materials, North American Edition (1992).

Nonionic lathering surfactants useful herein include those selected fromthe group consisting of alkyl glucosides, alkyl polyglucosides,polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucroseesters, amine oxides, and mixtures thereof.

Alkyl glucosides and alkyl polyglucosides are useful herein, and can bebroadly defined as condensation products of long chain alcohols, e.g.,C8-30 alcohols, with sugars or starches or sugar or starch polymers,i.e., glycosides or polyglycosides. These compounds can be representedby the formula (S)_(n)—O—R wherein S is a sugar moiety such as glucose,fructose, mannose, and galactose; n is an integer of from about 1 toabout 1000, and R is a C8-30 alkyl group. Examples of long chainalcohols from which the alkyl group can be derived include decylalcohol, cetyl alcohol, stearyl alcohol, lauryl alcohol, myristylalcohol, oleyl alcohol, and the like. Preferred examples of thesesurfactants include those wherein S is a glucose moiety, R is a C8-20alkyl group, and n is an integer of from about 1 to about 9.Commercially available examples of these surfactants include decylpolyglucoside (available as APG 325 CS from Henkel) and laurylpolyglucoside (available as APG 600CS and 625 CS from Henkel). Alsouseful are sucrose ester surfactants such as sucrose cocoate and sucroselaurate.

Other useful nonionic surfactants include polyhydroxy fatty acid amidesurfactants, more specific examples of which include glucosamides,corresponding to the structural formula:

wherein: R¹ is H, C₁-C₄ alkyl, 2-hydroxyethyl, 2-hydroxy-propyl,preferably C₁-C₄ alkyl, more preferably methyl or ethyl, most preferablymethyl; R² is C₅-C₃₁ alkyl or alkenyl, preferably C₇-C₁₉ alkyl oralkenyl, more preferably C₉-C₁₇ alkyl or alkenyl, most preferablyC₁₁-C₁₅ alkyl or alkenyl; and Z is a polhydroxyhydrocarbyl moiety havinga linear hydrocarbyl chain with a least 3 hydroxyls directly connectedto the chain, or an alkoxylated derivative (preferably ethoxylated orpropoxylated) thereof. Z preferably is a sugar moiety selected from thegroup consisting of glucose, fructose, maltose, lactose, galactose,mannose, xylose, and mixtures thereof. An especially preferredsurfactant corresponding to the above structure is coconut alkylN-methyl glucoside amide (i.e., wherein the R²CO— moiety is derived fromcoconut oil fatty acids). Processes for making compositions containingpolyhydroxy fatty acid amides are disclosed, for example, in G.B. PatentSpecification 809,060, published Feb. 18, 1959, by Thomas Hedley & Co.,Ltd.; U.S. Pat. No. 2,965,576, to E. R. Wilson, issued Dec. 20, 1960;U.S. Pat. No. 2,703,798, to A. M. Schwartz, issued Mar. 8, 1955; andU.S. Pat. No. 1,985,424, to Piggott, issued Dec. 25, 1934.

Other examples of nonionic surfactants include amine oxides. Amineoxides correspond to the general formula R₁R₂R₃N→O, wherein R₁ containsan alkyl, alkenyl or monohydroxy alkyl radical of from about 8 to about18 carbon atoms, from 0 to about 10 ethylene oxide moieties, and from 0to about 1 glyceryl moiety, and R₂ and R₃ contain from about 1 to about3 carbon atoms and from 0 to about 1 hydroxy group, e.g., methyl, ethyl,propyl, hydroxyethyl, or hydroxypropyl radicals. The arrow in theformula is a conventional representation of a semipolar bond. Examplesof amine oxides suitable for use in this invention includedimethyl-dodecylamine oxide, oleyldi(2-hydroxyethyl)amine oxide,dimethyloctylamine oxide, dimethyl-decylamine oxide,dimethyl-tetradecylamine oxide, 3,6,9-trioxaheptadecyidiethylamineoxide, di(2-hydroxyethyl)tetradecylamine oxide,2-dodecoxyethyldimethylamine oxide,3-dodecoxy-2-hydroxypropyldi(3-hydroxypropyl)amine oxide,dimethylhexadecylamine oxide.

Nonlimiting examples of preferred nonionic surfactants for use hereinare those selected form the group consisting of C8-C14 glucose amides,C8-C14 alkyl polyglucosides, sucrose cocoate, sucrose laurate, lauramineoxide, cocoamine oxide, and mixtures thereof.

Cationic Lathering Surfactants

Cationic lathering surfactants can also be optionally included in thecompositions of the present invention. Suitable cationic latheringsurfactants include, but are not limited to, fatty amines, di-fattyquaternary amines, tri-fatty quaternary amines, imidazolinium quaternaryamines, and combinations thereof. Suitable fatty amines include monalkylquaternary amines such as cetyltrimethylammonium bromide. A suitablequaternary amine is dialklamidoethyl hydroxyethylmonium methosulfate.

Amphoteric Lathering Surfactants

The term “amphoteric lathering surfactant,” as used herein, is alsointended to encompass zwitterionic surfactants, which are well known toformulators skilled in the art as a subset of amphoteric surfactants.

A wide variety of amphoteric lathering surfactants can be used in thecompositions of the present invention. Particularly useful are thosewhich are broadly described as derivatives of aliphatic secondary andtertiary amines, preferably wherein the nitrogen is in a cationic state,in which the aliphatic radicals can be straight or branched chain andwherein one of the radicals contains an ionizable water solubilizinggroup, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.

Nonlimiting examples of amphoteric or zwitterionic surfactants are thoseselected from the group consisting of betaines, sultaines,hydroxysultaines, alkyliminoacetates, iminodialkanoates,aminoalkanoates, and mixtures thereof.

Examples of betaines include the higher alkyl betaines, such as cocodimethyl carboxymethyl betaine, lauryl dimethyl carboxymethyl betaine,lauryl dimethyl alphacarboxyethyl betaine, cetyl dimethyl carboxymethylbetaine, cetyl dimethyl betaine (available as Lonzaine 16SP from LonzaCorp.), lauryl bis-(2-hydroxyethyl)carboxymethyl betaine, oleyl dimethylgamma-carboypropyl betaine, laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethylsulfopropyl betaine, lauryl dimethyl sulfoethyl betaine, laurylbis-(2-hydroxyethyl)sulfopropyl betaine, amidobetaines andamidosulfobetaines (wherein the RCONH(CH₂)₃ radical is attached to thenitrogen atom of the betaine), oleyl betaine (available as amphotericVelvetex OLB-50 from Henkel), and cocamidopropyl betaine (available asVelvetex BK-35 and BA-35 from Henkel).

Examples of sultaines and hydroxysultaines include materials such ascocamidopropyl hydroxysultaine (available as Mirataine CBS fromRhone-Poulenc).

Preferred for use herein are amphoteric surfactants having the followingstructure:

wherein R¹ is unsubstituted, saturated or unsaturated, straight orbranched chain alkyl having from about 9 to about 22 carbon atoms.Preferred R¹ has from about 11 to about 18 carbon atoms; more preferablyfrom about 12 to about 18 carbon atoms; more preferably still from about14 to about 18 carbon atoms; m is an integer from 1 to about 3, morepreferably from about 2 to about 3, and more preferably about 3; n iseither 0 or 1, preferably 1; R² and R³ are independently selected fromthe group consisting of alkyl having from 1 to about 3 carbon atoms,unsubstituted or mono-substituted with hydroxy, preferred R² and R³ areCH₃; X is selected from the group consisting of CO₂, SO₃ and SO₄; R⁴ isselected from the group consisting of saturated or unsaturated, straightor branched chain alkyl, unsubstituted or monosubstituted with hydroxy,having from 1 to about 5 carbon atoms. When X is CO₂, R⁴ preferably has1 or 3 carbon atoms, more preferably 1 carbon atom. When X is SO₃ orSO₄, R⁴ preferably has from about 2 to about 4 carbon atoms, morepreferably 3 carbon atoms.

Examples of amphoteric surfactants of the present invention include thefollowing compounds:

Cetyl dimethyl betaine (this material also has the CTFA designationcetyl betaine)

Cocamidopropylbetaine

wherein R has from about 9 to about 13 carbon atoms

Cocamidopropyl hydroxy sultaine

wherein R has from about 9 to about 13 carbon atoms,

Examples of other useful amphoteric surfactants are alkyliminoacetates,and iminodialkanoates and aminoalkanoates of the formulasRN[(CH₂)_(m)CO₂M]₂ and RNH(CH₂)_(m)CO₂M wherein m is from 1 to 4, R is aC_(8-C) ₂₂ alkyl or alkenyl, and M is H, alkali metal, alkaline earthmetal ammonium, or alkanolammonium. Also included are imidazolinium andammonium derivatives. Specific examples of suitable amphotericsurfactants include sodium 3-dodecyl-aminopropionate, sodium3-dodecylaminopropane sulfonate, N-higher alkyl aspartic acids such asthose produced according to the teaching of U.S. Pat. No. 2,438,091; andthe products sold under the trade name “Miranol” and described in U.S.Pat. No. 2,528,378. Other examples of useful amphoterics includeamphoteric phosphates, such as coamidopropyl PG-dimonium chloridephosphate (commercially available as Monaquat PTC, from Mona Corp.).Also useful are amphoacetates such as disodium lauroamphodiacetate,sodium lauroamphoacetate, and mixtures thereof.

Preferred lathering surfactants are selected from the group consistingof anionic lathering surfactants selected from the group consisting ofammonium lauroyl sarcosinate, sodium trideceth sulfate, sodium lauroylsarcosinate, ammonium laureth sulfate, sodium laureth sulfate, ammoniumlauryl sulfate, sodium lauryl sulfate, ammonium cocoyl isethionate,sodium cocoyl isethionate, sodium lauroyl isethionate, sodium cetylsulfate, sodium monolauryl phosphates, ethoxylated monoalkyl phosphates,sodium cocoglyceryl ether sulfonate, sodium C₉-C₂₂ soap, andcombinations thereof; nonionic lathering surfactants selected from thegroup consisting of lauramine oxide, cocoamine oxide, decyl polyglucose,lauryl polyglucose, sucrose cocoate, C12-14 glucosamides, sucroselaurate, and combinations thereof; cationic lathering surfactantsselected from the group consisting of fatty amines, di-fatty quaternaryamines, tri-fatty quaternary amines, imidazolinium quaternary amines,and combinations thereof; amphoteric lathering surfactants selected fromthe group consisting of disodium lauroamphodiacetate, sodiumlauroamphoacetate, cetyl dimethyl betaine, cocoamidopropyl betaine,cocoamidopropyl hydroxy sultaine, and combinations thereof.

ASSOCIATED METHODS

Applicant has found that the compositions of the present invention areuseful in a variety of applications directed to enhancement ofproteinaceous substrates like skin, hair, nails, and cuticles. Theapplication that is targeted will depend upon the cosmetic benefit agentthat is attached to the bonding agent. It is expected, however, that askilled artisan is capable of envisioning the appropriate cosmeticbenefit agent of those disclosed herein that are commensurate with themethod of use being disclosed. The methods of use for the compositionsdisclosed and claimed herein include, but are not limited to: 1) methodsof increasing the substantivity of a cosmetic active to skin; 2) methodsof moisturizing skin; 3) methods of improving the natural appearance ofskin; 4) methods of applying a color cosmetic to skin; 5) methods ofdeodorizing skin; 6) methods of providing antiperspirant efficacy toskin; 7) methods of preventing, retarding, and/or treating wrinkles; 8)methods of providing UV protection to skin; 9) methods of preventing,retarding, and/or treating cellulite; 10) methods of preventing,retarding, and/or controlling the appearance of oil; and 11) methods ofmodifying the feel and texture of skin; 12) methods of providing evenskin tone; 13) methods of preventing, retarding, and/or treating theappear of spider vessels and varicose veins; 14) methods of masking theappearance of vellus hair on skin; 15) methods of concealing blemishesand/or imperfections in human skin, including acne, age spots, freckles,moles, scars, under eye circles, birth marks, post-inflammatoryhyperpigmentation, etc.; and 16) methods of preventing, retarding,and/or treating malodor of a mammal. Each of the methods discussedherein involve topical application of the claimed compositions on toproteinaceous substrates, particularly skin.

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. In the following examples,all ingredients are listed at an active level. The examples are givensolely for the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.

For each of the diazonium salt bonding agents listed below, m=1 to 100,n=1 to 100, y=1 to 20, and z=2to 500.

Example 1

Antioxidant-modified Bonding Agent—Modified Ascorbate

Example 2

Antioxidant-modified Bonding Agent—Modified Gallate

Example 3

Colorant-modified Bonding Agent—Modified FD&C Yellow 6

Example 4

Colorant-modified Bonding Agent—Modified D&C Red 36

Example 5

Colorant-modified Bonding Agent—Modified D&C Green 8

Example 6

Humectant-modified Bonding Agent—Modified Glycerol

Example 7

Humectant-modified Bonding Agent—Modified PEG

Example 8

Silicone-modified Bonding Agent

Example 9

Silicone-modified Bonding Agent

Example 10

Sunscreen-modified Bonding Agent—Modified benzophenone-3

Example 11

Sunscreen-modified Bonding Agent—Modified octyl methoxycinnamate

Example 12

A lipstick product is prepared by mixing the following ingredients asdetailed below.

Ingredient Wt % Polybutene 4.536 Lanolin Oil 18.342 OctoxyglycerylBehenate 18.342 Stearyl heptanoate 8.856 Jojoba oil 8.856 Castor oil21.78 Butylated hydroxytoluene 0.054 Butylated hydroxyanisole 0.054Microcrystalline Wax 6.84 Polyethylene 500 6.84 Modified D&C Red 36(from Example 2) 4.5 (Amphiphlic lipid phase) Lecithin 0.475 Cholesterol0.475 dicetyl phosphate 0.05

Recrystallize modified D&C Red 36 using the single solvent method. Millmodified D&C Red 36 with Castor oil until desired Particle size isreached. Mixing of the different compounds is performed at a temperaturebetween 100-120 C. with stirring until fully homogenous. Heatamphiphilic lipid phase to 100 C. under nitrogen, add phases together,mill until uniform, mold, and cool.

Example 13

A foundation compact product is prepared by mixing the followingingredients as indicated below.

Phase Silicone Elastomer Compact Wt % A TiO2 silicone treated 5.25 AHydrophobic Yellow Iron Oxide Slurry (55% Pigment, 0.80 16.15%Cyclomethicone, 28.85% Dimethicone Copolyol) A Hydrophobic Red IronOxide Slurry (70% pigment, 0.31 10.7% cyclomethicone, 19.3% DimethiconeCopolyol) A Hydrophobic Black Iron Oxide Slurry (65% pigment, 0.12 13.2%cyclomethicone, 21.8% Dimethicone Copolyol) A Hydrophobic Talc 2.36 ATiO2 -MT100T (micronized) 0.16 A DC245 (cyclomethicone) 74.96 A DC5225C(dimethicone copolyol - 10% active) 0.31 B Silicone Elastomer 2.40 Bpropylparaben (preservative) 0.00 B Modified Glycerol (from Example 4)7.08 C Ozokerite Wax 6.25

The pigment slurries are created by combining the pigment, wetting agent(cyclomethicone), and dispersant (copolyol) and milling to the desiredparticle size. Ingredients in phase A are added together and high shearmilled until the desired particle size. Phase B ingredients are added tophase A ingredients and mixed until uniform. The mixture of phase A &Bis heated while mixing to 85-90 C. Phase C is added and mixed untilcompletely melted and the mixture is uniform. The mixture is then pouredinto a mold.

Example 14

A lip gel product is prepared by combining the following ingredients asdetailed below.

Ingredient Wt % Silicone elastomer 4.0 cyclomethicone 83.0 DimethiconeFluid 4.5 Modified D&C Green 8 (from Example 3) 6 Modified FD&C Yellow 6(from Example 1) 2.5

All Ingredients are mixed together using low to medium shear.

Example 15

A lip balm product is prepared by combining the following ingredients asdetailed below.

Phase Ingredient Wt % A Petrolatum 10.0 A Modified Glycerol (from 10.0Example 4) A Silicone elastomer 3.4 A cyclomethicone 64.3 A Dimethiconecopolyol 5.0 A Preservative 0.3 B Ozokerite wax 7.0

Ingredients in phase A are added together and mixed using low shearuntil uniform. Phase A is heated to 85-90 C. while mixing. Phase B isadded and mixed until uniform. This mixture is then poured into a mold.

Example 16

A moisturizing lotion is prepared by mixing the ingredients as detailedbelow.

Ingredient Wt % Main Water Phase USP Water 63.77435 Disodium EDTA 0.100Arlatone 2121 1.00 Part D - Particulate Premix (D) USP Water 5.000 (D)Glycerine 6.930 (D) Kobo Titanium Dioxide 0.544 Part A - NeutralizationPremix (A) USP Water 3.013 (A) Sodium Hydroxide 0.0125 Part B -Niacinamide Premix (B) USP Water 5.000 (B) Panthenol 0.500 (B) ModifiedAscorbate (from 2.000 Example 8) (B) FD&C Yellow No. 5 0.00115 (B) FD&CRed No. 40 0.00050 (C) Sefa Cottonate 0.670 (C) Isopropyl Isostearate1.330 (C) Tocopherol Acetate 0.500 (C) Permethyl 101A 3.000 (C) CetylAlcohol CO-1695 0.720 (C) Adol 62 0.480 (C) Nipigin A 0.200 (C) UenoPropylparaben NF 0.100 (C) Emersol 132 0.100 (C) Myrj 59 0.100 Part E(E) Sepigel 2.500 Q2-1403 2.000 Benzyl Alcohol 0.250 Fiery 5 0.175

In an appropriate container, prepare the Neutralization Premix. Add partA ingredients to container and mix with a stir bar until homogenous. Inan appropriate container prepare Part D (Particulate Premix). Mix bymixer until homogenous. In an appropriate container, prepare themodified ascorbate premix. Add Part B ingredients into container, exceptFD&C Yellow/Red. Heat to no higher than 40° C. while mixing untilmodified ascorbate is dissolved. Add FD&C Yellow/Red. Mix untildissolved. Prepare the Oil Phase. Add part C ingredients to oil phaseexcept Permethyl 101A and begin heating to 70-80° C. while mixingMaintain Temperature once heated. Prepare the water phase. Add USP waterto appropriate pyrex beaker, and begin heating to 70-80 C. while mixingwith a prop blade at 250-500 rpm. When water phase is between 70-80° C.add Disodium EDTA and Arlatone 2121 to beaker and allow to dissolve. Mixat least 5 minutes. When Oil & Water phases are between 70-80° C. beginto mill water phase. Slowly add oil phase to water phase while milling.Mill for 2-3 min. Add Particulate premix(part D) slowly, by hand pouringAdd neutralization premix (part A) slowly. Cool batch to 60° C. and addsepigel. Switch to U-blade once formula looks smooth. Cool batch to 50°C., then add modified ascorbate premix, Benzyl alcohol and Q2-1402. Coolbatch to 40° C. with periodic spatula mixing to insure homogeneity. Whentemperature reaches 40° C., add fragrance. Mill for 2-3 minutes.

Example 17

A solid antiperspirant stick of the present invention is prepared asfollows:

Ingredient Wt % Modified Gallate (from Example 9) 8.0 Stearyl Alcohol10.0 Hydrogenated Castor Oil-mp 86 degrees C. 4.0 AluminumChlorohydroxide 40.0 Isopar “V”¹ 37.0 Fragrance 1.0 ¹(Isopar “V” Avg.Mol. Wt. 197 B.P. Range, 255-301 degrees C.)

In a suitable vessel, neat, chemically synthesized modified ascorbate isdissolved using an appropriate solvent. The modified asdcorbate is thenrecrystallized by sublimation method. Next, the recrystallized modifiedascorbate is milled to the appropriate particle size.

In separate vessel containing a heat source, the isoparaffin liquids,the water-insoluble liquid emollients, the surface active agent, and thewater-insoluble waxes are heated to a temperature sufficient to form asolution of these materials. Next, the aluminum chlorohydroxide is addedwith gentle agitation, followed by the recrystallized modified ascorbateand remaining ingredients. The solution is mixed until a homogenoussuspension is formed. The suspension is cooled to a temperature abovethe solidification point and is then poured into suitable containers. Anantiperspirant composition, comprised as above, is applied to theunderarm area of a human subject, and reduces the perspiration in theapplied area.

Example 18

A long wearing eye shadow is prepared including the followingingredients that are mixed as detailed below.

Ingredient Wt % Pearl Mica CF 4.41 Glycerol Ester of Tall Oil Rosin 3.00GE SFE 839 Cross-linked Siloxane Elastomer gel¹ 44.6 PolyethyleneAC-617A 5.46 Beeswax White, Flakes 3.00 Propylparaben, NF 0.10 Tenox BHA0.20 Bentone 38 CF or Type 5.40 Propylene Carbonate 1.00 Phenoxyethanol0.80 Modified D&C Green 8 (from Example 3) 0.18 Talc 2755 3.00 MagnesiumCarbonate 309 2.00 Glyceryl Tribehenate 2.00 Paraffin Wax 1.50 ModifiedSilicone (from one of Examples 10 or 11) 1.30 Vanillin 0.01 Lecithin,Liquid 0.54 Aluminum Starch Octenyl Succinate 5.00 Pigment 16.5 ¹5%Dimethicone/vinyl dimethicone cross-polymer in cyclomethicone.

Example 19

A long wearing sunscreen product is prepared as detailed below.

Ingredient Wt % Water QS100 Glycerine 3.00 Disodium EDTA 0.10 MethylParaben 0.25 Sepigel 305 2.00 Octyl Salicylate 5.00 ModifiedBenzophenone-3 (from Example 6) 2.00 Modified octyl methoxycinnamate(from 1.50 Example 7) Isohexadecane 2.00 Steareth-21 0.80 Stearetch-20.10 Cetyl alcohol 0.80 Stearyl Alcohol 0.80 Behenyl Alcohol 0.80 PropylParaben 0.15

Prepare a water phase by combining the water, glycerin, disodium EDTA,methyl paraben in an appropriate vessel with mixing and heating toapproximately 75° C. Prepare the oil phase by combining the modifiedbenzophenone-3, octyl methoxycinnamate, isohexadecane, cetyl alcohol,stearyl alcohol, propyl paraben , octyl salicyclate, steareth-21,steareth-2, and behenyl alcohol into a separate vessel with mixing andheating to approximately 75° C. Mix the oil phase into the water phasewith shearing to form an emulsion. Cool the emulsion to 60° C. withshearing and add Sepigel 305. Slowly stir the emulsion and cool toapproximately 30° C., and package as desired.

Example 20

A long wearing sunscreen product is made as detailed below.

Ingredient Wt % Water QS100 Glycerine 2.00 Disodium EDTA 0.10 MethyParaban 0.25 Sepigel 305 2.50 2-Phenyl-Benzimidazole 5-Sulphonic Acid1.00 Triethanolamine 0.50 Octyl Salicylate 3.00 Modified Benzophenone-3(from example 6) 2.00 2-ethylhexyl-p-methoxycinnamate 1.33 Isohexadecane2.00 Cetyl alcohol 0.70 Stearyl Alcohol 0.70 Propyl Paraben 0.15Modified PEG-100 (from Example 5) 0.10

Prepare a water phase by combining the water, glycerin, disodium EDTA,methyl paraben in an appropriate vessel with mixing and heating toapproximately 75° C. Prepare the oil phase by combining the modifiedbenzophenone-3, 2-ethylhexyl-p-methoxycinnamate, isohexadecane, cetylalcohol, stearyl alcohol, propyl paraben, octyl salicyclate, andmodified PEG-100 into a separate vessel with mixing and heating toapproximately 75° C. Mix the oil phase into the water phase withshearing to form an emulsion. Cool the emulsion to 60° C. with shearingand add Sepigel 305, 2-phenyl-benzimidazole-5-sulphonic acid, andtriethanolamine. Slowly stir the emulsion and cool to approximately 30°C., and package as desired.

What is claimed is:
 1. A cosmetic composition comprising: a) a safe andeffective amount of a diazonium salt bonding agent having the structure

 wherein X represents a cosmetic benefit agent; and b) a cosmeticallyacceptable carrier for the bonding agent wherein the composition isadministered topically to a mammalian proteinaceous substrate andwherein the bonding agent reacts with a protein contained in thesubstrate such that the bonding agent is covalently attached to thesubstrate.
 2. The composition of claim 1 wherein the compositioncomprises from about 0.001% to about 25%, by weight of the composition,of the bonding agent.
 3. The composition of claim 2 wherein thecomposition comprises from about 0.1% to about 15%, by weight of thecomposition, of the bonding agent.
 4. The composition of claim 1 whereinX is selected from the group consisting of absorbents, anti-acneactives, anti-caking agents, anti-cellulite agents, anti-foaming agents,anti-fungal actives, anti-inflammatory actives, anti-microbial actives,anti-oxidants, antiperspirant/deodorant actives, anti-skin atrophyactives, anti-viral agents, anti-wrinkle actives, artificial tanningagents and accelerators, astringents, barrier repair agents, binders,buffering agents, bulking agents, chelating agents, colorants, dyes,enzymes, essential oils, film formers, flavors, fragrances, humectants,hydrocolloids, light diffusers, nail enamels, opacifying agents, opticalbrighteners, optical modifiers, particulates, perfumes, pH adjusters,sequestering agents, skin conditioners/moisturizers, skin feelmodifiers, skin protectants, skin sensates, skin treating agents, skinexfoliating agents, skin lightening agents, skin soothing and/or healingagents, skin thickeners, sunscreen actives, topical anesthetics, vitamincompounds, and combinations thereof.
 5. The composition of claim 1wherein X is attached to said bonding agent via a chemical linkercomprising one or more hydrocarbon chains containing heteroatoms.
 6. Thecomposition of claim 5 wherein said heteroatoms are selected from thegroup consisting of S, N, Se, O, substituted or unsubstituted aryls, Si,SiO, siloxane “D” groups [{(CH₃)}—Si—O₃], siloxane “M” groups{(CH₃)₃}—Si—O], and siloxane “T” groups [{(CH₃)}—Si—O_(3/2)].
 7. Thecomposition of claim 1 wherein said composition is in the form of a skinmoisturizing product.
 8. The composition of claim 1 wherein saidcomposition is in the form of a lipstick product.
 9. A method ofincreasing the substantivity of a cosmetic active to skin wherein saidmethod comprises topically applying the composition of claim 1 to skin.10. A method of moisturizing skin wherein the method comprises topicallyapplying the composition of claim 7 to skin.
 11. A method of improvingthe natural appearance of skin wherein said method comprises topicallyapplying the composition of claim 1 to skin.
 12. A method of applying acolor cosmetic to skin wherein said method comprises topically applyingthe composition of claim 1 to skin wherein X is a colorant.
 13. A methodof deodorizing skin wherein said method comprises topically applying thecomposition of claim 1 to skin wherein X is a deodorant active.
 14. Amethod of providing antiperspirant efficacy to skin wherein said methodcomprises topically applying the composition of claim 1 to skin whereinX is an antiperspirant active.
 15. A method of preventing, retarding,and/or treating wrinkles wherein said method comprises topicallyapplying the composition of claim 1 to skin wherein X is an anti-wrinkleactive.
 16. A method of providing UV protection to skin wherein saidmethod comprises topically applying the composition of claim 1 to skinwherein X is a sunscreen.
 17. A method preventing, retarding, and/ortreating cellulite wherein said method comprises topically applying thecomposition of claim 1 to skin wherein X is an anti-cellulite agent.